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Vanadium fluorides with novel crystal–chemical features and interesting physical properties can be prepared by solvothermal synthetic routes. The title compound, guanidinium hexafluoridovanadate(III), has a cubic structure (space group
Pa), exhibiting isolated regular VF
6 octahedral units, which are hydrogen bonded to protonated guanidinium moieties. Although the VF
6 octahedral units are not linked directly together, there are structural similarities between this crystal structure and those of the wider family of perovskite materials, in particular, hybrid perovskites based on extended ligands such as cyanide. In this context, the octahedral tilt system of the present compound is of interest and demonstrates that unusual tilt systems can be mediated
via `molecular' linkers which allow only supramolecular rather than covalent interactions.
Supporting information
CCDC reference: 1530543
Data collection: CrystalClear-SM Expert (Rigaku, 2014); cell refinement: CrystalClear-SM Expert (Rigaku, 2014); data reduction: CrystalClear-SM Expert (Rigaku, 2014); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012).
Triguanidinium hexafluoridovanadate(III)
top
Crystal data top
(CH6N3)3[VF6] | Mo Kα radiation, λ = 0.71075 Å |
Mr = 345.20 | Cell parameters from 800 reflections |
Cubic, Pa3 | θ = 2.5–25.3° |
a = 14.095 (3) Å | µ = 0.78 mm−1 |
V = 2800.2 (18) Å3 | T = 173 K |
Z = 8 | Block, green |
F(000) = 1408 | 0.08 × 0.07 × 0.05 mm |
Dx = 1.638 Mg m−3 | |
Data collection top
Rigaku SCXmini diffractometer | 778 reflections with I > 2σ(I) |
Detector resolution: 14.7059 pixels mm-1 | Rint = 0.093 |
profile data from φ–scans | θmax = 25.3°, θmin = 2.5° |
Absorption correction: multi-scan | h = −16→16 |
Tmin = 0.727, Tmax = 1.000 | k = −16→14 |
16185 measured reflections | l = −16→16 |
853 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | All H-atom parameters refined |
wR(F2) = 0.161 | w = 1/[σ2(Fo2) + (0.089P)2 + 0.3869P] where P = (Fo2 + 2Fc2)/3 |
S = 1.32 | (Δ/σ)max < 0.001 |
853 reflections | Δρmax = 0.44 e Å−3 |
83 parameters | Δρmin = −0.70 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
V1 | 0.0000 | 0.0000 | 0.0000 | 0.0124 (5) | |
V2 | 0.0000 | 0.0000 | 0.5000 | 0.0125 (5) | |
F1 | −0.02491 (10) | 0.02779 (10) | 0.13294 (10) | 0.0191 (5) | |
F2 | 0.02648 (11) | 0.02032 (10) | 0.36612 (10) | 0.0193 (5) | |
N1 | 0.02433 (19) | 0.35925 (18) | 0.25208 (15) | 0.0254 (7) | |
N2 | 0.01649 (17) | 0.22012 (18) | 0.16926 (18) | 0.0243 (6) | |
N3 | 0.04043 (18) | 0.21871 (18) | 0.33114 (17) | 0.0248 (6) | |
C1 | 0.0273 (3) | 0.2656 (2) | 0.25114 (15) | 0.0187 (7) | |
H1 | 0.0158 (19) | 0.389 (2) | 0.201 (2) | 0.023 (7)* | |
H2 | 0.0294 (18) | 0.391 (2) | 0.304 (2) | 0.023 (7)* | |
H3 | 0.008 (2) | 0.255 (2) | 0.117 (3) | 0.030 (10)* | |
H4 | 0.013 (2) | 0.165 (3) | 0.171 (2) | 0.023 (8)* | |
H5 | 0.038 (3) | 0.248 (2) | 0.383 (3) | 0.040 (10)* | |
H6 | 0.0386 (19) | 0.164 (2) | 0.333 (2) | 0.017 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
V1 | 0.0124 (5) | 0.0124 (5) | 0.0124 (5) | 0.0002 (2) | 0.0002 (2) | 0.0002 (2) |
V2 | 0.0125 (5) | 0.0125 (5) | 0.0125 (5) | −0.0002 (2) | −0.0002 (2) | 0.0002 (2) |
F1 | 0.0222 (8) | 0.0191 (8) | 0.0159 (8) | 0.0005 (7) | 0.0016 (6) | −0.0009 (6) |
F2 | 0.0223 (9) | 0.0200 (8) | 0.0157 (8) | −0.0014 (7) | 0.0015 (6) | 0.0007 (6) |
N1 | 0.0413 (15) | 0.0169 (14) | 0.0179 (15) | −0.0017 (10) | −0.0005 (10) | −0.0010 (9) |
N2 | 0.0387 (14) | 0.0144 (12) | 0.0199 (13) | −0.0015 (10) | 0.0010 (10) | 0.0001 (10) |
N3 | 0.0390 (15) | 0.0175 (13) | 0.0179 (12) | 0.0013 (10) | 0.0001 (10) | 0.0004 (10) |
C1 | 0.0184 (14) | 0.0199 (14) | 0.0177 (15) | −0.0022 (12) | 0.0020 (9) | −0.0011 (9) |
Geometric parameters (Å, º) top
V1—F1i | 1.9461 (15) | V2—F2 | 1.9448 (15) |
V1—F1ii | 1.9461 (15) | N1—C1 | 1.321 (4) |
V1—F1iii | 1.9461 (15) | N1—H1 | 0.85 (3) |
V1—F1iv | 1.9461 (15) | N1—H2 | 0.86 (3) |
V1—F1v | 1.9461 (15) | N2—C1 | 1.329 (4) |
V1—F1 | 1.9462 (15) | N2—H3 | 0.89 (4) |
V2—F2vi | 1.9448 (15) | N2—H4 | 0.78 (3) |
V2—F2vii | 1.9448 (15) | N3—C1 | 1.320 (3) |
V2—F2viii | 1.9448 (15) | N3—H5 | 0.84 (4) |
V2—F2ix | 1.9448 (15) | N3—H6 | 0.77 (3) |
V2—F2x | 1.9448 (15) | | |
| | | |
F1i—V1—F1ii | 180.00 (13) | F2vi—V2—F2x | 180.0 |
F1i—V1—F1iii | 90.93 (6) | F2vii—V2—F2x | 89.14 (6) |
F1ii—V1—F1iii | 89.07 (6) | F2viii—V2—F2x | 90.86 (6) |
F1i—V1—F1iv | 89.07 (6) | F2ix—V2—F2x | 89.14 (6) |
F1ii—V1—F1iv | 90.93 (6) | F2vi—V2—F2 | 89.14 (6) |
F1iii—V1—F1iv | 89.07 (6) | F2vii—V2—F2 | 90.86 (6) |
F1i—V1—F1v | 90.93 (6) | F2viii—V2—F2 | 89.14 (6) |
F1ii—V1—F1v | 89.07 (6) | F2ix—V2—F2 | 180.0 |
F1iii—V1—F1v | 90.93 (6) | F2x—V2—F2 | 90.86 (6) |
F1iv—V1—F1v | 180.00 (9) | C1—N1—H1 | 120 (2) |
F1i—V1—F1 | 89.07 (6) | C1—N1—H2 | 121.9 (19) |
F1ii—V1—F1 | 90.93 (6) | H1—N1—H2 | 118 (3) |
F1iii—V1—F1 | 180.0 | C1—N2—H3 | 118.1 (19) |
F1iv—V1—F1 | 90.93 (6) | C1—N2—H4 | 118 (2) |
F1v—V1—F1 | 89.07 (6) | H3—N2—H4 | 124 (3) |
F2vi—V2—F2vii | 90.86 (6) | C1—N3—H5 | 119 (2) |
F2vi—V2—F2viii | 89.14 (6) | C1—N3—H6 | 122 (2) |
F2vii—V2—F2viii | 180.00 (8) | H5—N3—H6 | 117 (3) |
F2vi—V2—F2ix | 90.86 (6) | N3—C1—N2 | 121.1 (3) |
F2vii—V2—F2ix | 89.14 (6) | N3—C1—N1 | 119.7 (2) |
F2viii—V2—F2ix | 90.86 (6) | N2—C1—N1 | 119.1 (2) |
Symmetry codes: (i) −z, −x, −y; (ii) z, x, y; (iii) −x, −y, −z; (iv) y, z, x; (v) −y, −z, −x; (vi) −y, z−1/2, −x+1/2; (vii) z−1/2, x, −y+1/2; (viii) −z+1/2, −x, y+1/2; (ix) −x, −y, −z+1; (x) y, −z+1/2, x+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F2xi | 0.85 (3) | 2.16 (3) | 2.906 (3) | 147 (3) |
N1—H2···F1xi | 0.86 (3) | 2.12 (3) | 2.876 (3) | 146 (3) |
N2—H3···F2iv | 0.89 (4) | 2.03 (4) | 2.879 (3) | 159 (3) |
N2—H4···F1 | 0.78 (3) | 2.08 (3) | 2.820 (3) | 160 (3) |
N3—H5···F1x | 0.84 (4) | 2.13 (4) | 2.919 (3) | 157 (3) |
N3—H6···F2 | 0.77 (3) | 2.09 (3) | 2.846 (3) | 169 (3) |
Symmetry codes: (iv) y, z, x; (x) y, −z+1/2, x+1/2; (xi) −x, y+1/2, −z+1/2. |
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